Acryloyloxy and methacryloyloxy group-containing condensation polymers

Abstract

Organic solvent soluble, acryloyloxy and methacryloyloxy group-containing, condensation polymers are crosslinkable and useful for providing chemical, solvent, sand abrasion resistant articles. The condensation polymers are polyesters or polyurethanes having an acryloyloxy or methacryloyloxyalkanediol component that is uncontaminated by hydroxyl group-containing compounds having one, three, or more hydroxyl groups or compounds in which the acryloyloxy or methacryloyloxy group is attached to a secondary carbon atom.

I claim: 
     
       1. A condensation polymer comprising the reaction product of (1) diols, at least one of which is an acryloyloxyalkanediol or methacryloyloxyalkanediol of the formula ##STR20##  in which R is hydrogen or methyl, R 3  is hydrogen or a lower alkyl group having 1 to 4 carbon atoms, or ##STR21## R 4  is hydrogen or one or more of monovalent saturated or unsaturated linear, branched, or cyclic aliphatic groups having 1 to 24 carbon atoms, or aromatic groups having 6 to 18 carbon atoms, all of which can be optionally substituted by groups unreactive in esterification reactions, that is uncontaminated by hydroxyl group-containing compounds having one, three, or more hydroxyl groups and compounds in which the acryloyloxy and methacryloyloxy group is attached to a secondary carbon atom, and     (2) an organic diisocyanate, said reaction product being a linear polymer     
     
     
       2. The condensation polymer according to claim 1 wherein said acryloyloxyalkanediol and methacryloyloxyalkanediol is present in an amount in the range of 5 to 100 weight percent. 
     
     
       3. The condensation polymer according to claim 1 wherein said acryloyloxyalkanediol and methacryloyloxyalkanediol is a 2-acryloyloxymethyl-1,3-propanediol or a 2-methacryloyloxymethyl-1,3-propanediol. 
     
     
       4. The condensation polymer according to claim 1 wherein said acryloyloxyalkanediol and methacryloyloxyalkanediol is selected from the group consisting of 2,2-bis(acryloyloxymethyl)-1-3-propanediol,   2-acryloyloxymehhyl-1,3-propanediol   2-acryloyloxymethyl-2-methyl-1,3-propanediol   2-acryloyloxymethyl-2-ethyl-1,3-propanediol,   2,2-bis(methacryloyloxymethyl)-1,3-propanediol,   2-methacryloyloxymethyl-1,3-propanediol,   2-methacryloyloxymethyl-2-methyl-1,3-propanediol, and   2-methacryloyloxymethyl-2-ethyl-1,3-propanediol.   
     
     
       5. The condensation polymer according to claim 1 wherein said organic diisocyanate is an aliphatic, aromatic, or heterocyclic diisocyanate. 
     
     
       6. A condensation polymer having the formula ##STR22## wherein W and Z are terminal groups; R 1  is one or more divalent organic groups;   Y is --NH--;   a is a number having a value 2 to 200;   R 2  is at least one divalent organic group which is the saturated or unsaturated residue provided by removal of two hydroxyl groups from (1) a polymeric diol selected from the group consisting of polyetherdiols, polyamidediols, polyurethanediol,, and polysiloxanediols having a molecular weight of up to 150000, (2) a monomeric diol which is a linear, branched, or cyclic aliphatic diol having 2 to 12 carbon atoms, (3) an aryl or alkaryldiol having 6 to 15 carbon atoms, or (4) at least one 1,3-propanediol represented by the formula: ##STR23##  in which R 3  is hydrogen or lower alkyl having 1 to 4 carbon atoms or ##STR24##  and R 4  is one or more of hydrogen and monovalent saturated or unsaturated linear, branched, or cyclic aliphatic groups having 1to 24 carbon atoms, or aromatic groups having 6 to 18 carbon atoms all of which can be optionally substituted by groups unreactive in esterification reactions;    provided that at least 5 weight percent of all diols is a 1,3-propanediol of formula II in which R 4  is --CH═CH 2  or ##STR25##  said 1,3-propanediol being uncontaminated by hydroxyl group-containing compounds having one, three, or more hydroxyl groups and compounds in which the acryloyloxy and methacryloyloxy group is attached to a secondary carbon atom, and said condensation polymer being a linear polymer.   
     
     
       7. The condensation polymer according to claim 6 wherein R 1  is a divalent aliphatic group having 2 to 40 carbon atoms or a divalent aromatic group having 5 to 24 carbon atoms. 
     
     
       8. A condensation polymer according to claim 6 in which Y is --NH-- to provide a polyurethane. 
     
     
       9. A condensation polymer according to claim 7 wherein R 1  is substituted by non-interfering groups selected from the group consisting of individual catenated, ##STR26## in which R 10  is lower alkyl of 1 to 4 carbon atoms. 
     
     
       10. A process for the preparation of an acryloyloxy and methacryloyloxy group-containing linear condensation polymer comprising the steps: (a) providing a polymerization mixture of (1) one or more of organic diisocyanates and   (2) one or more of polymeric and monomeric diols of which 5 to 100 percent by weight are diols represented by the formula: ##STR27##  in which R is hydrogen or methyl R 3  is hydrogen, lower alkyl, or ##STR28##  wherein said R 4  is one or more of hydrogen and monovalent saturated or unsaturated linear, branched, or cyclic aliphatic groups having 1 to 24 carbon atoms, or aromatic groups having 6 to 18 carbon atoms, all of which can be optionally substituted by groups unreactive in esterification reactions;        said diol being uncontaminated by hydroxyl group-containing compounds having one, three, or more hydroxyl groups and compounds in which the acryloyloxy and methacryloyloxy group is attached to a secondary carbon atom,   (b) heating the polymerization mixture at an effective temperature for a time sufficient to effect polymerization.   
     
     
       11. The process according to claim 10 wherein said organic diisocyanate of step (a)(1) is an aliphatic, aromatic, or heterocyclic diisocyanate. 
     
     
       12. The process according to claim 10 wherein said polymeric diol of step (a)(2) is selected from the group consisting of polyetherdiols, polyesterdiols, polyolefindiols, polyamidediols, polyurethanediols, and polysiloxanediols, and said monomeric diol is selected from aliphatic diols having 2 to 12 carbon atoms and aryl and alkaryl diols having 6 to 15 carbon atoms. 
     
     
       13. The process according to claim 10 wherein said polymerization mixture further comprises a molecular weight-controlling amount of monofunctional alcohol, or organic isocyanate. 
     
     
       14. The process according to claim 10 wherein said polymerization mixture further comprises an effective amount of at least one of a heat or radiation activated polymerization initiator, an organic solvent, a catalyst, a dye, a pigment, a fiber, a particle, or an organic polymer.